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| United States Patent |
6,031,118
|
|
van Amerongen
, et al.
|
February 29, 2000
|
Stanol ester composition and production thereof
Abstract
Stanol fatty acid ester composition comprising at least 85% of stanol
(saturated) fatty acid esters in which at least 85% of the fatty acid
groups are saturated. Also claimed is a process for the preparation of
stanol fatty acid esters, by hardening phytosterol fatty acid or a mixture
thereof, or as an alternative, a process for the preparation of stanol
fatty acid esters by esterification of phytosterols or a mixture thereof,
followed by the hardening of the so obtained phytosterol fatty acid
esters.
| Inventors:
|
van Amerongen; Marnix P. (Vlaardingen, NL);
Lievense; Lourus Cornelis (Valinhos, BR)
|
| Assignee:
|
Lipton, Division of Conopco, Inc. (Englewood Cliffs, NJ)
|
| Appl. No.:
|
135720 |
| Filed:
|
August 18, 1998 |
Foreign Application Priority Data
| Current U.S. Class: |
552/544; 426/602; 426/603; 426/611; 552/545 |
| Intern'l Class: |
C07J 009/00 |
| Field of Search: |
514/182
552/544,545
426/602,603,611
|
References Cited
U.S. Patent Documents
| 4806632 | Feb., 1989 | McCoy et al. | 536/124.
|
| 5502045 | Mar., 1996 | Miettinen et al. | 514/182.
|
| 5734070 | Mar., 1998 | Tacke et al. | 554/144.
|
| Foreign Patent Documents |
| 792 107 | May., 1996 | EP.
| |
| 743 014 | Nov., 1996 | EP.
| |
| 62-055040 | Oct., 1987 | JP.
| |
| 1 405 346 | Sep., 1973 | GB.
| |
| 92/19640 | Nov., 1992 | WO.
| |
| 96/38047 | Dec., 1996 | WO.
| |
| 98/01126 | Jan., 1998 | WO.
| |
| 98/06405 | Feb., 1998 | WO.
| |
| 98/19556 | May., 1998 | WO.
| |
Primary Examiner: Reamer; James H.
Attorney, Agent or Firm: McGowan, Jr.; Gerard J.
Claims
What is claimed is:
1. Stanol fatty acid ester composition comprising at least 85% of stanol
fatty acid esters in which at least 85% of the fatty acid groups are
saturated.
2. Stanol fatty acid ester composition according to claim 1, wherein at
least 90% of the fatty acid groups are saturated fatty acid groups.
3. Process for the preparation of stanol fatty acid esters, by hardening
phytosterol fatty acid esters or a mixture thereof.
4. Process for the preparation of stanol fatty acid esters by
esterification of phytosterols or a mixture thereof, followed by the
hardening of the so obtained phytosterol fatty acid esters.
5. Process according to claim 4, wherein both esterification and hardening
step are performed in the absence of a solvent.
6. Process according to claim 3, wherein the hardening treatment is carried
out such that at least 85% of the sterol fatty acid esters is hardened.
7. Food product comprising a stanol fatty acid ester according to claim 1.
8. Food product according to claim 7, wherein at least 1 wt %, and
preferably at least 2 wt % stanol equivalents (present as stanol fatty
acid esters) are present.
9. Food product according to claim 7, wherein the food product is a fat
based food product.
10. Food product according to claim 9, wherein the fat based food product
is a yellow fat spread, which preferably comprises at least 5 wt % of the
stanol equivalents (present as stanol fatty acid esters).
11. Food product according to claim 9, wherein the fat or fat blend used in
the product comprises at least 30 wt %, and preferably at least 45 wt % of
PUFA rich triglycerides, calculated on the total weight of the fat present
in the product.
Description
BACKGROUND OF THE INVENTION
The present invention concerns a method for the production of stanol fatty
acid esters, a stanol fatty acid ester composition, and the use thereof in
food products, in particular in fat based food products in amounts
sufficient to obtain a blood cholesterol lowering effect if the food
product is used according to the common needs of the consumer.
Fatty acid esters of phytosterols and/or phytostanols are hydrolyzed in the
gut and the subsequent free phytosterols and/or phytostanols will inhibit
the absorption of cholesterol thereby lowering the blood cholesterol. Free
phytosterols and/or phytostanols themselves are hardly absorbed.
Indications in literature are that phytostanols are absorbed even in a
lesser extend than phytosterols. The use of phytostanols in fat based food
products to lower blood cholesterol could therefore be preferred over the
use of phytosterols.
In U.S. Pat. No. 5,502,045 (Raision Tehtaat Oy AB) a substance of
beta-sitostanol fatty acid ester is described produced by 1. solvent
hardening of beta-sitosterol followed by 2. esterification of the formed
beta-sitostanol with fatty acids. The so formed mixture of beta-sitostanol
fatty acid esters can be used as such or added to a food.
There are several disadvantages to this production method, of which the
most severe is that the beta-sitosterol should first be solubilized in a
solvent (e.g. ethylacetate, butanol, ethanol) before the hardening of the
sterol can be performed. Because the solubility of beta-sitosterol, or
phytosterols in general, in solvents is rather limited, the hardening step
is relatively expensive operation because of high solvent costs and high
costs of hardening equipment of relative large volume. Moreover, the
solvents needs to be recovered after the hardening process is completed,
and suitable locations for above hardening process will be limited because
of environmental regulations. Furthermore, in a process aiming at the
production of a food ingredient, removal of all solvents is essential,
this making the process even more expensive.
SUMMARY OF THE INVENTION
It has now been found that phytostanol fatty acid esters can be suitably
prepared by the esterification of phytosterols, followed by hardening of
the so formed phytosterol fatty acid esters. This method has the advantage
that no solvents in the hardening step are needed since the
phytosterol-esters are in a liquid form by themselves. Moreover, besides
this method is solvent free and environmentally friendly, and thus not
requiring specific legal admissions, it is also more cost effective due to
the fact that less raw materials, equipment and labour is required. In
another embodiment, the stanol fatty acid esters are prepared by hardening
phytosterol fatty acid esters or a mixture thereof.
Where in this application sterols are mentioned, phytosterols
(4-desmethylsterols, 4-monomethylsterols and 4,4'-dimethylsterols, and/or
mixtures thereof) are meant. These sterols can be found in several plant
materials.
Sources are described in, for example, PCT/EP96/02344. For this invention,
a preference exists for sterols from vegetable oil.
For obtaining the sterolesters before hardening is carried out, the sterols
are esterified with one or more C.sub.2-24 fatty acids. For the purpose of
the invention the term C.sub.2-24 fatty acid refers to any molecule
comprising a C.sub.2-24 main chain and at least one acid group. Although
not preferred within the present context the C.sub.2-24 main chain may be
partially substituted or side chains may be present. Preferably, however
the C.sub.2-24 fatty acids are linear molecules comprising one or two acid
group(s) as endgroup(s). Most preferred are linear C.sub.8-22 fatty acids
as occur in natural oils. Suitable esterification conditions are for
example described in WO 92/19640.
Suitable examples of any such fatty acids are acetic acid, propionic acid,
butyric acid, caproic acid, caprylic acid, capric acid. Other suitable
acids are for example citric acid, lactic acid, oxalic acid and maleic
acid. Preferred are lauric acid, palmitic acid, stearic acid, arachidic
acid, behenic acid, oleic acid, cetoleic acid, erucic acid, elaidic acid,
linoleic acid and linolenic acid.
Most preferred are the C18 polyunsaturated, monounsaturated or saturated
fatty acids like stearic acid, oleic acid, elaidic, linoleic acid,
alpha-linolenic acid and gamma-linolenic acid, since after fully hardening
of sterolesters comprising these fatty acids, the fatty acid part will be
the saturated stearic acid, which has a neutral effect on blood
cholesterol.
When desired a mixture of fatty acids may be used. For example it is
possible to use a natural occurring fat or oil as a source of the fatty
acid and to carry out the esterification via an interesterification
reaction. Most preferred are fatty acid mixtures containing high amounts
(>70%) of C18 polyunsaturated, monounsaturated or saturated fatty acids
such as fatty acid mixtures of sunflower, safflower, rapeseed, linseed,
linola and/or soybean.
The fatty acid ester stanols so obtained are also subject of this
invention. These stanol esters, of which >85%, preferably >90%, and most
preferably >95% are saturated stanol esters which are formed by the
hardening of esterified sterols, will be of a very different nature when
compared to the stanol esters prepared by hardening and subsequent
esterification.
These saturated fatty acid stanol esters were found to have stronger
structuring properties than stanolesters mixtures comprising mainly mono-
or poly-unsaturated fatty acids, due to their higher melting points. By
using the so produced stanolesters with saturated fatty acids, the amount
of hardstock required to make a spreadable product out of above mentioned
liquid oils can be more reduced than with stanolesters mixtures comprising
mainly mono- or poly-unsaturated fatty acids, thereby potentially
optimizing the amount of PUFA rich glycerides in the product further, and
thereby compensating the saturated fatty acid part of the stanol ester
mixture applied in the product.
The stanol (saturated) fatty acid ester (mixture) of this invention may
still comprise some unhardened and/or unesterified sterols and/or sterol
esters. It is preferred, however, that the stanol ester mixture of the
invention comprises at least 85% of the stanol (saturated) fatty acid
esters, and preferably at least 90%, with a most preferred embodiment
being found in 95 to about 100% being stanol (saturated) fatty acid
esters. In another embodiment, the invention concerns stanol fatty acid
ester compositions comprising at least 85% of stanol fatty acid esters in
which at least 85% of the fatty acid groups are saturated.
Also subject of the invention are food products, in particular fat based
food products, comprising the stanol (saturated) fatty acid ester
(mixtures) in all embodiments set forth above. It is preferred that the
food product comprises at least 1%, and preferably at least 2% and more
preferably at least 5% stanol equivalents (present as stanol fatty acid
esters).
The use of these stanolesters in food products has the advantage that no
regular intake of supplements is needed, and that through the normal food
pattern, a significant reduction of the cholesterol level can be obtained.
The use of the stanol esters of this invention is in particular preferred
in fat based food products, this type of food products being part of the
daily menu in most western world countries.
Fat based food products are food products (partially) based on fat and
regarded by the consumer, as `fatty type of products`. Examples are yellow
fat spreads (containing vegetable fat and/or animal fat such as
butterfat), dressings, coffee-creamer, shortenings, cooking and frying
oils, fillings and toppings, ice-cream and the like. These products in
most cases comprise a particular amount of fat.
In some cases, however, products are still regarded as `fatty type of
products`, despite a replacement of part or even all the fat by fat
replacers. Fat based food products in which the fat is partially or
completely replaced by fat replacers are also covered by the term fat
based food products of this invention.
The food products as such are common products in the western world, and are
used by consumers on a daily basis in amounts different for each
individual. The invention is in particular very suitable for yellow fat
spreads, dressings, cheese, shortenings, cooking and frying oils and ice
cream, with a preference for yellow fat spreads, mayonnaise, dressings,
shortenings, cooking and frying oils. On the basis of habits of the
consumer in the western world, the preferred applications are yellow fat
spreads (including margarines, butter and low fat spreads) and dressings.
Yellow fat spreads, for this invention, can comprise 0 (zero) to 90% fat
(usually 5-80%). Dressings can comprise 0 to 85% fat (usually 5-80%),
shortenings, cooking and frying oil more than 95% fat.
In such products, a further preference exists for the use of stanol
equivalents (present as stanol fatty acid esters) of this invention of at
least 3 wt. %, and more preferred of at least 5 wt. %, with a further
preference for at least 7 wt. %.
The preparation of the fat based food products comprising the saturated
stanol fatty acid esters of the invention can be carried out in any
suitable manner commonly known. Suitably, the stanol esters, which will
often be a mixture of different stanol esters, can be added and dissolved
to the fat prior to combining with the aqueous phase of the product to be
prepared.
In a preferred embodiment, the food product is a yellow fat spread
comprising 0 to 80% fat and at least 1 wt. %, preferably at least 2 wt. %
and more preferably at least 5 wt % stanol equivalents (present as stanol
esters prepared according to the invention). In its most preferred
embodiment, the amount of stanol equivalents is at least 5%, with optimal
results found when the amount of stanol is in the range of 7-15%.
The invention is in particular suitable for low fat spreads having a fat
level in the range of 0-40%, where the amount of cholesterol level
reducing fat is low. However, another preference exists for higher fat
level spreads (60-80% fat), as a very significant reduction of cholesterol
level in the blood serum can be obtained when high PUFA fat level fats are
used, and where the fat in the spread is not optimized on PUFA, to add the
cholesterol lowering effect upon use to such spreads.
The fat that is applied in these fat based food products can be any fat,
such as dairy fat and/or vegetable fat. However, if fat is present, for
health reasons the use of one or more vegetable fat sources is preferred.
In particular, the use of liquid fats is preferred. The fat can be one
single fat or a blend. The use of fat compositions comprising a
considerable amount of PUFA rich triglycerides in addition to the use of
the stanol (saturated) fatty acid ester (mixture) is in particular
considered highly beneficial. For example, oils of sunflower, safflower,
rapeseed, linseed, linola and/or soybean can be used in a preferred
embodiment. Also the fat compositions mentioned in Netherlands patent
documents no. Nl 143115, Nl 178559, Nl 155436, Nl 149687, Nl 155177,
European patent documents EP 41303, EP 209176, EP 249282, and EP 470658
are highly suitable.
If a fat blend is used, it is preferred that it comprises at least 30%, and
more preferred at least 45% of poly-unsaturated fatty acids, based on the
total weight amount of the fat in the fat based food product. So, a strong
effect on the cholesterol lowering effect is obtained if use is made of
the stanol (saturated) fatty acid esters as set forth in this application
in a food product in which a fat blend comprising at least 30 wt. % of
PUFA rich triglycerides is used.
As fat spreads are a commonly and daily used product in western food eating
habits, a preference exists for the use of the stanol (saturated) fatty
acid esters in all the preferred embodiments as set forth above, in fat
spreads.
Where butterfat is used for preparing spreads of the invention, or where
the spreads are butter, it is preferred that the amount of stanol
equivalents is at least 5 wt. % with optimal results found when the amount
of stanol equivalents is in the range of 10-15 wt. %. As the consumption
of butter is considered less beneficial for consumers health, the present
invention is in particular suitable for making butter or butter-melanges
containing spreads, as the negative effect associated with the butter
consumption can be minimized or even reversed.
EXAMPLES
Example 1a
Hydrogenation of Steryl Esters
A mixture of sterols derived from soybean oil distillates esterified with
sunflowerseed oil fatty acids (to an esterification degree >85%) was
hydrogenated on laboratory scale. As catalyst 5 wt % Pd on activated
carbon was used. To 0.5 kg of the sterylesters 2 g of catalyst was added
and the mixture was heated to 90 degrees C. under reduced pressure 5-30
mbar.
The hydrogenation was carried out at 90 degrees C. and at 3 bar hydrogen
pressure. After 90 minutes approximately 40% of the theoretical amount of
hydrogen was absorbed and again 2 g of catalyst was added. After 7.5 hours
approx. 80% of the theoretical amount of hydrogen was absorbed and 2 g of
catalyst was added and the temperature increased to 95-115 degrees C.
Finally, after 11 hours of reaction approx. 100% of the theoretical amount
of hydrogen was absorbed. At that moment no extra hydrogen was absorbed
anymore and the hydrogenation was ended.
The major part of the catalyst was removed by filtration over a paper
filter. The remaining part of the catalyst was removed by applying 2%
Hyflow and filtration over a paper filter.
Analysis indicated that a hardening conversion of over 90% was achieved.
Example 2a
Preparation of a Spread 70% Fat (Stanol Esters Ex. 1a)
Refined sunflower oil (65% PUFA as linoleic acid) was enriched with
esterified stanols as obtained from Example 1a (to a total stanol
equivalent concentration of 45%). Of this stanol-ester concentrate, 22
parts were mixed with 35 parts of normal refined sunflower oil, 15 parts
of refined rapeseed oil and 8 parts of a refined interesterified mixture
of 65 parts fully hardened palm oil and 35 parts fully hardened palm
kernel oil. To this fat blend, small amounts of soybean lecithin,
monoglyceride, flavours and beta-carotene solution were added.
To 18 parts water, small amounts of whey protein powder, flavour, and
citric acid were added to obtain a pH of 4.8.
80 parts of the fat phase composition (containing 70% of fat) and 20 parts
of the aqueous phase composition were mixed and kept at 60 degrees C. The
mixture was then passed through a Votator line with 2 scraped surface heat
exchangers (A-units) and 1 stirred crystallizer (C-unit) in AAC-sequence
operating at 800, 800 and 100 rpm respectively. The product leaving the
C-unit had a temperature of 11 degrees C. It was filled into tubs and
stored at 5 degrees C. A good and stable, high PUFA, high fat-continuous
spread enriched with 10% stanol equivalents (mainly present as C18:0
stanol esters) was obtained.
Example 3a
Preparation of a Spread 40% (Stanol Esters Ex. 1a)
Refined sunflower oil (65% PUFA as linoleic acid) was enriched with
esterified stanols as obtained from Example 1a (to a total stanol
equivalent concentration of 45%). Of this stanol-ester concentrate, 22
parts were mixed with 23 parts of normal refined sunflower oil and with 5
parts of a refined interesterified mixture of 50 parts fully hardened palm
oil and 50 parts fully hardened palm kernel oil. To this fat blend small
amounts of soybean lecithin, monoglyceride and beta-carotene solution were
added.
To 44 parts water, gelatin and small amounts of whey protein powder,
flavours, preservative and citric acid were added to obtain a pH of 4.7.
50 parts of the fat phase composition (containing 40% of fat) and 48 parts
of the aqueous phase composition were mixed and kept at 60 degrees C. The
mixture was then passed through a Votator line with 2 scraped surface heat
exchangers (A-units) and 2 stirred crystallizers (C-unit), in
ACAC-sequence operating at 500, 1000, 600 and 100 rpm respectively. The
product leaving the last C-unit had a temperature of 10 degrees C. It was
filled into tubs and stored at 5 degrees C. A good and stable, high PUFA,
low fat-continuous spread enriched with 10% stanol equivalents (mainly
present as C18:0 stanol esters) was obtained.
Example 4a
Preparation of a Dressing (Stanol Esters Ex. 1a)
49 parts of water is mixed with 11 parts of various flavour components,
preservatives, thickeners and emulsifiers. The mixture is thoroughly mixed
in a stainless steel stirred vessel. To this aqueous mixture 20 parts of
sunflower oil (65% PUFA as linoleic acid) enriched with 40% stanol
equivalents present as stanol esters as obtained from Example 1a is added.
To above oil in water mixture, 20 parts of normal refined sunflower oil is
added, thoroughly mixed for an additional 15 min, to obtain a
pre-emulsion. The pre-emulsion is brought into a colloid mill (Prestomill
PM30) and processed at a split-size between level 15 and 20 and a
throughput between level 4 and 6. A good and stable water continuous
dressing enriched with 8% stanol equivalents (mainly present as C18:0
stanol esters) is obtained.
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